CN114832653A - Preparation method of solvent-resistant PTFE composite nanofiltration membrane - Google Patents
Preparation method of solvent-resistant PTFE composite nanofiltration membrane Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 74
- 229920001343 polytetrafluoroethylene Polymers 0.000 title claims abstract description 57
- 239000004810 polytetrafluoroethylene Substances 0.000 title claims abstract description 57
- 238000001728 nano-filtration Methods 0.000 title claims abstract description 41
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000002904 solvent Substances 0.000 title claims abstract description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000000243 solution Substances 0.000 claims abstract description 47
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims abstract description 30
- 239000000178 monomer Substances 0.000 claims abstract description 25
- 230000003213 activating effect Effects 0.000 claims abstract description 24
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 22
- 239000012982 microporous membrane Substances 0.000 claims abstract description 21
- 239000003960 organic solvent Substances 0.000 claims abstract description 16
- 235000011056 potassium acetate Nutrition 0.000 claims abstract description 15
- 150000001263 acyl chlorides Chemical class 0.000 claims abstract description 14
- 150000001412 amines Chemical class 0.000 claims abstract description 14
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 12
- URXNVXOMQQCBHS-UHFFFAOYSA-N naphthalene;sodium Chemical compound [Na].C1=CC=CC2=CC=CC=C21 URXNVXOMQQCBHS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000002791 soaking Methods 0.000 claims abstract description 11
- 230000004913 activation Effects 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 12
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 7
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 229920002873 Polyethylenimine Polymers 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 5
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 4
- 230000014759 maintenance of location Effects 0.000 claims description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 4
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims description 4
- 239000012510 hollow fiber Substances 0.000 claims description 3
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 2
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 claims description 2
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims description 2
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 claims description 2
- FYXKZNLBZKRYSS-UHFFFAOYSA-N benzene-1,2-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC=C1C(Cl)=O FYXKZNLBZKRYSS-UHFFFAOYSA-N 0.000 claims description 2
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 claims description 2
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 2
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 239000002585 base Substances 0.000 abstract description 11
- 239000002253 acid Substances 0.000 abstract description 4
- 239000003513 alkali Substances 0.000 abstract description 4
- 230000007935 neutral effect Effects 0.000 abstract description 3
- 239000002344 surface layer Substances 0.000 abstract description 3
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- 210000004379 membrane Anatomy 0.000 description 24
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- 238000000614 phase inversion technique Methods 0.000 description 1
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- 239000012085 test solution Substances 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 229940045860 white wax Drugs 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/36—Polytetrafluoroethene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
- B01D69/105—Support pretreatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Abstract
The invention discloses a preparation method of a solvent-resistant PTFE composite nanofiltration membrane, which comprises the following specific steps: cleaning a polytetrafluoroethylene microporous membrane by using ethanol and soaking the polytetrafluoroethylene microporous membrane in the ethanol; activating the surface of the polytetrafluoroethylene microporous membrane by using potassium acetate activating solution or sodium naphthalene activating solution; immersing the activated base film in an aqueous solution of an amine monomer, standing for a period of time, taking out, and airing in the air; immersing the dried base film in an organic solution of acyl chloride monomer, standing for a period of time, taking out, and placing in the air for drying; the prepared nanofiltration membrane organic solvent has the characteristics of stable neutral property, insolubility, small swelling degree, difficult peeling between a surface layer and a base membrane and the like, can be used in harsh systems such as organic solvents, strong acid and strong alkali, high temperature and the like for a long time, and greatly increases the application scenes of the nanofiltration membrane.
Description
Technical Field
The invention belongs to the technical field of composite nanofiltration membranes, and particularly relates to a preparation method of a solvent-resistant PTFE composite nanofiltration membrane.
Background
Nanofiltration is a membrane separation technology between ultrafiltration and reverse osmosis, has the advantages of high selectivity, low energy consumption, simple operation and the like, and is widely applied to the fields of spinning, printing and dyeing, medicines, foods, petroleum, chemical industry, papermaking, water treatment and the like. In the industrial field, most of aqueous solutions contain organic solvents, and a nanofiltration membrane resistant to the solvents is urgently needed for application. With the continuous development and growth of the industry in China and the continuous improvement of the environmental protection requirement, the demand of the market in China on the solvent-resistant nanofiltration membrane is continuously increased, and the continuous improvement of the productivity of the solvent-resistant nanofiltration membrane industry in China is promoted. However, the solvent-resistant nanofiltration membrane industry in China is weak in overall competitiveness, high-end product productivity is poor, and the structure of the industry needs to be continuously optimized in the future. The application requirements of the nanofiltration membrane in the fields of chemical industry, papermaking, printing and dyeing, medicine, food and the like are continuously increased, a large amount of organic solvents are used in the production process of downstream industries, sewage is directly discharged, and the harm to the environment is large.
Polytetrafluoroethylene (PTFE, abbreviated as "plastic king") is a high molecular polymer prepared by polymerizing tetrafluoroethylene as a monomer. White wax, translucency, heat resistance and cold resistance are excellent, and the glass can be used for a long time at minus 180-260 ℃. The material has the characteristics of acid resistance, alkali resistance and various organic solvents resistance, and is almost insoluble in all solvents. Meanwhile, the polytetrafluoroethylene has the characteristic of high temperature resistance. In recent years, PTFE separation membranes have been rapidly developed and advanced, and research and development of novel PTFE membrane separation materials are actively conducted in some scientific research institutes in China, and PTFE hollow fiber membranes have been used in industrial fields.
Currently, most of the SRNF membranes for commercial use are prepared by a phase inversion method, and have disadvantages of low permeability and selectivity and limited chemical and thermal stability, which limit the application of the SRNF membranes.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a solvent-resistant PTFE composite nanofiltration membrane.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a solvent-resistant PTFE composite nanofiltration membrane comprises the following specific steps:
(S1), washing the polytetrafluoroethylene microporous membrane by using ethanol and soaking the polytetrafluoroethylene microporous membrane in the ethanol;
(S2), activating the surface of the polytetrafluoroethylene microporous membrane by using potassium acetate activating solution or sodium naphthalene activating solution;
(S3) immersing the activated base membrane in an aqueous solution of amine monomers, standing for a period of time, taking out, and airing in the air;
(S4) immersing the dried base membrane in an organic solution of acyl chloride monomer, standing for a period of time, taking out, and drying in the air;
and (S5) putting the processed membrane into an oven for drying treatment to obtain the PTFE composite nanofiltration membrane.
Preferably, in the step (S1), the ethanol concentration is 50-100%, and the soaking time is 5-120 minutes.
Preferably, the potassium acetate activation solution in the step (S2) comprises potassium acetate, ethanol, sodium hydroxide and deionized water, wherein the mass fraction of the potassium acetate is 5-20%, the mass fraction of the ethanol is 30-75%, the mass fraction of the sodium hydroxide is 1-5%, the mass fraction of the deionized water is 25-50%, the activation time is 5-120 minutes, and the activation temperature is 25-80 ℃.
Preferably, the composition of the sodium naphthalene activation solution in the step (S2) includes tetrahydrofuran, sodium and naphthalene, wherein the mass fraction of the tetrahydrofuran is 80-95%, the mass fraction of the sodium is 1-5%, the mass fraction of the naphthalene is 5-15%, the activation time is 10-60 seconds, and the activation temperature is room temperature.
Preferably, in the step (S3), the aqueous solution of the amine monomer is 0.2-5% by mass, and the retention time is 10-900 seconds, wherein the amine substance in the aqueous solution of the amine monomer is one or a mixture of piperazine, polyethyleneimine, m-phenylenediamine, ethylenediamine, hexamethylenediamine, triethylamine, o-xylylenediamine, m-xylylenediamine, p-xylylenediamine, and methyldiethanolamine.
Preferably, the organic solution of the acyl chloride monomer in the step (S4) is an organic solution with a mass fraction of 0.2-5%, and the retention time is 5-300 seconds, and the acyl chloride substance in the organic solution of the acyl chloride monomer is one or a mixture of trimesoyl chloride, isophthaloyl chloride, terephthaloyl chloride and phthaloyl chloride.
Preferably, the organic solvent of the organic solution in the step (S4) is any one of n-hexane, toluene, n-octane, ethyl acetate, isooctane, and n-heptane.
Preferably, in the step (S5), the oven drying temperature is 50 to 120 ℃, and the drying time is 1 to 30 minutes.
Preferably, the PTFE composite nanofiltration membrane is a polytetrafluoroethylene hollow fiber membrane or a polytetrafluoroethylene flat membrane, the pore diameter of the polytetrafluoroethylene microporous membrane is 0.02-0.2 micron, and the porosity is 50-85%.
Has the advantages that:
the method for preparing the PTFE composite nanofiltration membrane has the advantages of simple production flow and easy industrialization, the solvent resistance and the separation performance of the prepared solvent-resistant PTFE composite nanofiltration membrane are excellent, the nanofiltration membrane prepared by the method has the characteristics of stable organic solvent neutral property, insolubility, small swelling degree, difficult peeling of a surface layer and a base membrane and the like, can be used in harsh systems such as organic solvents, strong acid and strong alkali, high temperature and the like for a long time, and greatly increases the application scenes of the nanofiltration membrane.
Drawings
FIG. 1 is a block flow diagram of the overall manufacturing process of the present invention.
Detailed Description
The following further illustrates a specific embodiment of the preparation method of the solvent-resistant PTFE composite nanofiltration membrane in accordance with the present invention with reference to fig. 1. The preparation method of the solvent-resistant PTFE composite nanofiltration membrane is not limited to the description of the following examples.
Example 1
(S1) washing a teflon microporous membrane with 75% ethanol and soaking in ethanol;
(S2) activating the surface of the polytetrafluoroethylene microporous membrane by using a potassium acetate activating solution, wherein the potassium acetate activating solution comprises the following components: 15% of potassium acetate, 50% of ethanol, 5% of sodium hydroxide and 30% of deionized water, wherein the activation time is 30 minutes, and the activation temperature is 80 ℃;
(S3) immersing the activated base membrane in an aqueous solution of amine monomers, wherein the solution is a 0.2% mixed solution (75% of polyethyleneimine, 20% of piperazine and 5% of ethylenediamine), standing for 60 seconds, taking out, and airing in the air;
(S4) immersing the dried basement membrane in an organic solution of acyl chloride monomers, wherein the organic solution is 0.5% (80% trimesoyl chloride and 20% terephthaloyl chloride), the organic solvent is n-hexane, and after staying for 15 seconds, taking out the basement membrane and placing the basement membrane in the air for drying;
(S5) finally, putting the processed membrane into an oven for post-processing, wherein the oven temperature is 60 ℃, and the processing time is 20 minutes, so as to obtain the PTFE composite nanofiltration membrane.
Example 2
(S1) washing the teflon microporous membrane with 100% ethanol and soaking in ethanol;
(S2) activating the surface of the polytetrafluoroethylene microporous membrane by using a sodium naphthalene activating solution, wherein the sodium naphthalene activating solution comprises the following components: 85% of tetrahydrofuran, 3% of sodium and 12% of naphthalene, wherein the activation time is 20 seconds, and the activation temperature is room temperature;
(S3) immersing the activated base membrane in an aqueous solution of amine monomers, wherein the solution is a 0.5% mixed solution (60% of polyethyleneimine, 30% of piperazine and 10% of m-phenylenediamine), standing for 90 seconds, taking out, and airing in the air;
(S4) immersing the dried basement membrane in an organic solution of acyl chloride monomers, wherein the organic solution is 0.5% trimesoyl chloride, the organic solvent is n-hexane, standing for 20 seconds, taking out, and drying in the air;
(S5) finally, putting the processed membrane into an oven for post-processing, wherein the oven temperature is 120 ℃, and the processing time is 1 minute, so as to obtain the PTFE composite nanofiltration membrane.
Example 3
(S1) washing the teflon microporous membrane with 100% ethanol and soaking in ethanol;
(S2) activating the surface of the polytetrafluoroethylene microporous membrane by using a sodium naphthalene activating solution, wherein the sodium naphthalene activating solution comprises the following components: tetrahydrofuran 90%, sodium 2% and naphthalene 8%, the activation time is 60 seconds, and the activation temperature is room temperature;
(S3) immersing the activated basement membrane in an aqueous solution of amine monomers, wherein the solution is a 0.5% mixed solution (80% polyethyleneimine and 20% piperazine), standing for 180 seconds, taking out, and airing in the air;
(S4) immersing the dried basement membrane in an organic solution of acyl chloride monomers, wherein the organic solution is 0.5% (75% trimesoyl chloride and 25% terephthaloyl chloride), the organic solvent is heptane, standing for 10 seconds, taking out, and drying in the air;
(S5) finally, putting the processed membrane into an oven for post-processing, wherein the oven temperature is 80 ℃, and the processing time is 30 minutes, so as to obtain the PTFE composite nanofiltration membrane.
Example 4
(S1) washing a teflon microporous membrane with 50% ethanol and soaking in ethanol;
(S2) activating the surface of the polytetrafluoroethylene microporous membrane by using a potassium acetate activating solution, wherein the potassium acetate activating solution comprises the following components: 10% of potassium acetate, 60% of ethanol, 1% of sodium hydroxide and 29% of deionized water, wherein the activation time is 30 minutes, and the activation temperature is 60 ℃;
(S3) immersing the activated base membrane in an aqueous solution of amine monomers, wherein the solution is a 2.0% mixed solution (60% of piperazine, 35% of m-phenylenediamine and 5% of ethylenediamine), standing for 30 seconds, taking out, and airing in the air;
(S4) immersing the dried basement membrane in an organic solution of acyl chloride monomers, wherein the organic solution is 0.5% of trimesoyl chloride, the organic solvent is n-hexane, and after the organic solution stays for 30 seconds, the basement membrane is taken out and placed in the air to be dried;
(S5) finally, putting the processed membrane into an oven for post-processing, wherein the oven temperature is 105 ℃, and the processing time is 5 minutes, so as to obtain the PTFE composite nanofiltration membrane.
Example 5
(S1) washing the teflon microporous membrane with 100% ethanol and soaking in ethanol;
(S2) activating the surface of the polytetrafluoroethylene microporous membrane by using a sodium naphthalene activating solution, wherein the sodium naphthalene activating solution comprises the following components: 80% of tetrahydrofuran, 5% of sodium and 15% of naphthalene, wherein the activation time is 10 seconds, and the activation temperature is room temperature;
(S3) immersing the activated base membrane in an aqueous solution of amine monomers, wherein the solution is a 0.5% mixed solution (70% of polyethyleneimine and 30% of m-phenylenediamine), standing for 120 seconds, taking out, and airing in the air;
(S4) immersing the dried basement membrane in an organic solution of acyl chloride monomers, wherein the organic solution is 1.0% trimesoyl chloride, the organic solvent is heptane, standing for 10 seconds, taking out, and placing in the air for drying;
(S5) finally, putting the processed membrane into an oven for post-processing, wherein the oven temperature is 60 ℃, and the processing time is 30 minutes, so as to obtain the PTFE composite nanofiltration membrane.
The PTFE composite nanofiltration membranes prepared in examples 1-5 were tested as follows, wherein,
(1) and (3) testing conditions are as follows: testing after soaking in solvent, wherein the test solution has a concentration of 2000ppm, a test temperature of 25 deg.C, a test pressure of 0.6MPa, and a pH value of 7
(2) The rejection (R) is calculated as: r ═ Cf-Cp)/Cf × 100%
In the formula: cf-membrane influent concentration; concentration of Cp-film produced aqueous solution
(3) The formula for calculating the membrane flux (J) is: j is V/(T is multiplied by A)
Wherein J-membrane flux (L/m 2. h); v- -sample volume (L); t- -sample time (h); a- -effective area of film (m2)
TABLE 1
The data in the embodiments 1 to 5 and the data in the table 1 show that the method for preparing the PTFE composite nanofiltration membrane has the advantages of simple production process and easy industrialization, the prepared solvent-resistant PTFE composite nanofiltration membrane has excellent solvent resistance and separation performance, the nanofiltration membrane prepared by the method has stable organic solvent neutral property, has the characteristics of insolubility, small swelling degree, difficult peeling of a surface layer and a base membrane and the like, can be used in harsh systems such as organic solvents, strong acid, strong alkali, high temperature and the like for a long time, and greatly increases the application scenes of the nanofiltration membrane.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
Claims (9)
1. A preparation method of a solvent-resistant PTFE composite nanofiltration membrane is characterized by comprising the following steps: the method comprises the following specific steps:
(S1) washing a polytetrafluoroethylene microporous membrane by using ethanol and soaking the polytetrafluoroethylene microporous membrane in the ethanol;
(S2), activating the surface of the polytetrafluoroethylene microporous membrane by using potassium acetate activating solution or sodium naphthalene activating solution;
(S3) immersing the activated base membrane in an aqueous solution of amine monomers, standing for a period of time, taking out, and airing in the air;
(S4) immersing the dried base membrane in an organic solution of acyl chloride monomer, standing for a period of time, taking out, and drying in the air;
and (S5) putting the treated membrane into an oven for drying treatment to obtain the PTFE composite nanofiltration membrane.
2. The preparation method of the solvent-resistant PTFE composite nanofiltration membrane of claim 1, wherein the preparation method comprises the following steps: in the step (S1), the concentration of the ethanol is 50-100%, and the soaking time is 5-120 minutes.
3. The preparation method of the solvent-resistant PTFE composite nanofiltration membrane of claim 1, wherein the preparation method comprises the following steps: the potassium acetate activation solution in the step (S2) comprises potassium acetate, ethanol, sodium hydroxide and deionized water, wherein the mass fraction of potassium acetate is 5-20%, the mass fraction of ethanol is 30-75%, the mass fraction of sodium hydroxide is 1-5%, the mass fraction of deionized water is 25-50%, the activation time is 5-120 minutes, and the activation temperature is 25-80 ℃.
4. The preparation method of the solvent-resistant PTFE composite nanofiltration membrane of claim 1, wherein the preparation method comprises the following steps: the sodium naphthalene activation solution in the step (S2) comprises tetrahydrofuran, sodium and naphthalene, wherein the mass fraction of the tetrahydrofuran is 80-95%, the mass fraction of the sodium is 1-5%, the mass fraction of the naphthalene is 5-15%, the activation time is 10-60 seconds, and the activation temperature is room temperature.
5. The preparation method of the solvent-resistant PTFE composite nanofiltration membrane as claimed in claim 1, wherein the preparation method comprises the following steps: in the step (S3), the aqueous solution of the amine monomer is 0.2-5% by mass, and the retention time is 10-900 seconds, wherein the amine substance in the aqueous solution of the amine monomer is one or a mixture of piperazine, polyethyleneimine, m-phenylenediamine, ethylenediamine, hexamethylenediamine, triethylamine, o-xylylenediamine, m-xylylenediamine, p-xylylenediamine, and methyldiethanolamine.
6. The preparation method of the solvent-resistant PTFE composite nanofiltration membrane of claim 1, wherein the preparation method comprises the following steps: the organic solution of the acyl chloride monomer in the step (S4) is an organic solution with the mass fraction of 0.2-5%, the retention time is 5-300 seconds, and the acyl chloride substance in the organic solution of the acyl chloride monomer is one or a mixture of more of trimesoyl chloride, isophthaloyl chloride, terephthaloyl chloride and phthaloyl chloride.
7. The preparation method of the solvent-resistant PTFE composite nanofiltration membrane of claim 1, wherein the preparation method comprises the following steps: the organic solvent of the organic solution in the step (S4) is any one of n-hexane, toluene, n-octane, ethyl acetate, isooctane, and n-heptane.
8. The preparation method of the solvent-resistant PTFE composite nanofiltration membrane as claimed in claim 1, wherein the preparation method comprises the following steps: in the step (S5), the drying temperature of the oven is 50-120 ℃, and the drying time is 1-30 minutes.
9. The preparation method of the solvent-resistant PTFE composite nanofiltration membrane of claim 1, wherein the preparation method comprises the following steps: the PTFE composite nanofiltration membrane is a polytetrafluoroethylene hollow fiber membrane or a polytetrafluoroethylene flat membrane, the pore diameter of the polytetrafluoroethylene microporous membrane is 0.02-0.2 micrometer, and the porosity is 50-85%.
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| CN117024843A (en) * | 2023-07-23 | 2023-11-10 | 深圳赛兰仕科创有限公司 | Preparation method of ultralow-dielectric low-loss epoxy composite material |
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